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Many-Body
Pair Cluster
Potentials Potentials
Non-Linearity
Pair Cluster
Functionals Functionals
50
Harmonic
40
Exact
Energy (kcal/mole)
30
20
3rd order
polynomial
10
0
60 80 100 120 140 160 180
Angle
2/8/05 3.320/SMA5107: Atomistic Modeling of Materials G. Ceder and N Marzari
More complicated molecules
Draw cos(2)
and cos(3)
Energy
A
a r
c
Used when the four atoms defining the torsion are not in sequence
One given potential does not deal with changes in the coordination
of covalent bonds. Changes in coordination are done by changing
the potential ! ->
Hence: different potentials for sp2, sp3 sp carbon
Potentials good for:
Conformation (configuration) of molecules
Packing of molecules
Barriers between various conformations
Potentials not good for:
Chemical reactions (bond breaking)
Potentials lack polarization
r C q1q2
V(r) = A exp
6 +
r r
long-ranged electrostatic part is summed by Ewald method
qs
qn qn + q s = q ion
Two particles used per ion: core and shell, connected by a spring
Shell interacts with other shells through potentials
Cores and shells interact eletrostatically
Core and shell of one atom are coupled through a spring
2
Vion = kr
states of MgO
A consistent set of pair potentials has been derived empirically by fitting to the
experimentally measured lattice properties of a series of binary metal oxide. In contrast to
previous strategies, the potential parameters were optimized concurrently, utilizing
residuals from all structures in the series, each calculated from the energy-minimized
geometry. A more reliable determination of ion polarisabilities can thus be made.
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For metals
Bond energy depends very much on the number of bonds already made to an atom.
Such an effect is absent in pair potentials, which are by definition environment-
independent.
As a result, whenever bond-breaking in covalent materials is involved, the
result of a potential model should be interpreted cautiously.
Very good potentials have been fit to C-H and C-C bonds in various bonding
arrangements. These can be used to model conformational arrangements of
polymeric systems (where no bond-breaking is involved)
For oxides
Feb 8 2005 3.320 Atomistic Modeling of Materials -- Gerbrand Ceder and Nicola Marzari
Why do we need quantum mechanics ?
Nicola
NicolaMarzari:
Marzari:
Porphyrin
Porphyrinfrom http://www.chem.uit.no/KJEMI/publications2.html,Raman
fromhttp://www.chem.uit.no/KJEMI/publications2.html, Ramanspectra
spectra
From
FromMauri
Mauriand
andLazzeri
LazzeriPhys.
Phys.Rev.
Rev.Lett.
Lett.Paper
Paper
Feb 8 2005 3.320 Atomistic Modeling of Materials -- Gerbrand Ceder and Nicola Marzari
3) Dynamics, chemistry
Diels-Alder Reaction:
1,3-butadiene + ethylene cyclohexene
http://www.wag.caltech.edu/home-pages/jim/
Feb 8 2005 3.320 Atomistic Modeling of Materials -- Gerbrand Ceder and Nicola Marzari
Standard Model of Matter
Atoms are made by massive,
point-like nuclei
(protons+neutrons)
Feb 8 2005 3.320 Atomistic Modeling of Materials -- Gerbrand Ceder and Nicola Marzari
Material Properties From First-Principles
Feb 8 2005 3.320 Atomistic Modeling of Materials -- Gerbrand Ceder and Nicola Marzari
Bibliography
Richard M. Martin, Electronic Structure: Basic
Theory and Practical Methods, Cambridge
University Press (2004).
Feb 8 2005 3.320 Atomistic Modeling of Materials -- Gerbrand Ceder and Nicola Marzari
Wave-particle Duality
Waves have particle-like properties:
Photoelectric effect: quanta (photons) are
exchanged discretely
Energy spectrum of an incandescent body looks
like a gas of very hot particles
Particles have wave-like properties:
Electrons in an atom are like standing waves
(harmonics) in an organ pipe
Electrons beams can be diffracted, and we can
see the fringes
Feb 8 2005 3.320 Atomistic Modeling of Materials -- Gerbrand Ceder and Nicola Marzari
When is a particle like a wave ?
Wavelength momentum = Planck
p = h ( h = 6.6 x 10-34 J s )
http://www.kfunigraz.ac.at/imawww/vqm/
Feb 8 2005 3.320 Atomistic Modeling of Materials -- Gerbrand Ceder and Nicola Marzari
Quantum effects in the nuclear motion
The nature of the hydrated excess proton in water,
Marx, D., Tuckermann, M. E., Hutter, J., & Parrinello,
M. (1999). Nature (London) 397, 601-604
Feb 8 2005 3.320 Atomistic Modeling of Materials -- Gerbrand Ceder and Nicola Marzari
Mechanics of a Particle
2r
r
d r r r r r r (t )
m 2 = F (r ) = V (r ) r
dt v (t )
The sum of the kinetic and potential energy is conserved
Feb 8 2005 3.320 Atomistic Modeling of Materials -- Gerbrand Ceder and Nicola Marzari
Description of a Wave
The wave is an excitation (a
vibration): we need to know
the amplitude of the excitation
at every point and at every
instant
r
= (r , t )
Feb 8 2005 3.320 Atomistic Modeling of Materials -- Gerbrand Ceder and Nicola Marzari
Time-dependent Schrdingers equation
(Newtons 2nd law for quantum objects)
r
h 2
r r r (r , t )
( r , t ) + V ( r , t ) ( r , t ) = ih
2
2m t
Feb 8 2005 3.320 Atomistic Modeling of Materials -- Gerbrand Ceder and Nicola Marzari
Stationary Schrdingers Equation (I)
r
h 2
r r r (r , t )
( r , t ) + V ( r , t ) ( r , t ) = ih
*
2
2m t
Feb 8 2005 3.320 Atomistic Modeling of Materials -- Gerbrand Ceder and Nicola Marzari
Stationary Schrdingers Equation (II)
h 2
r r r
+ V (r ) (r ) = E (r )
2
2m
Feb 8 2005 3.320 Atomistic Modeling of Materials -- Gerbrand Ceder and Nicola Marzari
Interpretation of the Quantum
Wavefunction (Copenhagen)
r 2
(r , t ) is the probability of finding an electron
in r and t
2
r i r 2
(r ) exp( Et ) = (r )
h
Feb 8 2005 3.320 Atomistic Modeling of Materials -- Gerbrand Ceder and Nicola Marzari
Metal Surfaces (I)
Feb 8 2005 3.320 Atomistic Modeling of Materials -- Gerbrand Ceder and Nicola Marzari
Metal Surfaces (II)
Feb 8 2005 3.320 Atomistic Modeling of Materials -- Gerbrand Ceder and Nicola Marzari
Solutions in a Coulomb Potential:
the Periodic Table
http://www.orbitals.com/orb/orbtable.htm
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Feb 8 2005 3.320 Atomistic Modeling of Materials -- Gerbrand Ceder and Nicola Marzari